Catalytic and Electrochemical Release of Solar Energy Stored in Strained Organic Compounds

存储在应变有机化合物中的太阳能的催化和电化学释放

• 批准号: 392607742
• 负责人: Professor Dr. Julien Bachmann, Ph.D.
• 金额: --
• 依托单位: Institut für Chemie und Biochemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2018
• 资助国家: 德国
• 起止时间: 2017-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/392607742?language=en
• 关键词: Catalytic; Electrochemical; Release; Solar; Energy

We envision that solar energy conversion and storage could be integrated via intramolecular reactions in single molecule systems. Such processes would combine key features of photovoltaic and photochemical methods in the most simple and efficient manner. The prototypical example for such an intramolecular reaction is the photochemical conversion of norbornadiene (NBD) to its metastable valence isomer quadricyclane (QC), a single-photon, single-molecule process in which bond-breaking and bond-making events are simplified to the maximum. The reverse reaction from QC to NBD releases up to 100 kJ/mol, making QC a solar fuel with an energy density comparable to state-of-the-art batteries.This project aims at generating the fundamental knowledge to unleash the full potential of chemical energy storage in strained organic molecules. Three major challenges associated with the energy release reaction will be addressed: (1) Its catalytic triggering: Starting from a fundamental understanding of the catalytically triggered cycloreversion and its undesired side-reactions, such as dehydrogenation and C-C bond scission, we will aim at developing catalysts with enhanced selectivity and higher reversibility in the storage cycle. (2) Its electrochemical triggering: Based on a fundamental understanding of the electrochemically triggered cycloreversion, we will aim at improving the reversibility of the storage cycle by design of electrodes and electrochemical environments which limit undesired side-reactions and electrode fouling. (3) The direct conversion to electrical energy: As a grand challenge we envision an "energy-storing solar cell", i.e. the direct conversion of the chemical energy stored in QC to electrical energy. To this aim, we will design hybrid interfaces with appropriate electronic structure, chemical structure and electrochemical stability to demonstrate the feasibility of this new concept.To tackle these very ambitious goals, the groups of Bachmann, Libuda, and Papp have teamed up to combine their complementary expertise in surface science, in-situ spectroscopy, electrochemistry, and materials science. The project team will study the mechanism, kinetics, energetics and stability of the NBD/QC system and its derivatives in ultrahigh vacuum, at ambient pressure, at solid/liquid interfaces and under (photo)electrochemical conditions. Combining aspects of insight gained from single crystal studies, complex model catalysts, and nanostructured materials, we will obtain a detailed understanding of the energy release reaction and the factors that currently limit its reversibility. We will then use this knowledge to develop improved catalytic and electrochemical storage systems, i.e. combinations of molecules, materials, and methods enabling "single-photon, single-molecule" energy conversion and storage in a better controlled, more efficient, and more reversible fashion.

我们设想，太阳能转化和存储可以通过单分子系统中的分子内反应整合。这样的过程将以最简单和有效的方式结合光伏和光化学方法的关键特征。这种分子内反应的原型示例是将北丁二烯（NBD）的光化学转化到其亚稳态价异构体Quadricyclane（QC），这是一种单光子，单分子过程，其中简化了键合和键合的事件，从而最大程度地简化了键合的事件。从质量控制到NBD的反应反应最多可释放100 kJ/mol，使QC成为一种太阳能燃料，其能量密度可与最先进的电池相当。该项目旨在产生基本知识，以释放菌株有机分子中化学能量储存的全部潜力。将解决与能量释放反应相关的三个主要挑战：（1）其催化触发：从对催化触发的环循环及其不希望的副反应的基本了解开始，例如脱氢和C-C键的分裂，我们将旨在在存储周期中增强选择性和更高的稳定性催化剂。 （2）其电化学触发：基于对电化学触发的环循环的基本了解，我们将通过设计电极和电化学环境来改善存储周期的可逆性，从而限制了不希望的侧反应和电极构造。 （3）直接转换为电能：作为一个巨大的挑战，我们设想了一个“能量存储太阳能电池”，即将QC中存储的化学能的直接转换为电能。 To this aim, we will design hybrid interfaces with appropriate electronic structure, chemical structure and electrochemical stability to demonstrate the feasibility of this new concept.To tackle these very ambitious goals, the groups of Bachmann, Libuda, and Papp have teamed up to combine their complementary expertise in surface science, in-situ spectroscopy, electrochemistry, and materials science.项目团队将在超高真空中，在固体/液体界面和（照片）电化学条件下，在超高真空中研究NBD/QC系统及其衍生物的机制，动力学，能量和稳定性。结合了从单晶研究，复杂模型催化剂和纳米结构材料中获得的洞察力方面，我们将详细了解能量释放反应以及当前限制其可逆性的因素。然后，我们将使用这些知识来开发改进的催化和电化学存储系统，即分子，材料和方法的组合，以“单光子，单分子”能量转换和存储，以更好地控制，更有效，更有效，更可逆的方式。